Lakes of monoazo dyestuffs



Unite The present invention relates to color lakes of monoazo dyestuffs of the acylacetic acid amide series which contain one or two carboxylic acid and/or sulfonic acid groups which form lakes with divalent and multivalent metals, and apart from these groups and the enolizable CO group of the acylacetylamino radical, contain no watersolubilizing groups.

- The process for the production of the new color lakes consists in treating monazo dyestuffs of the acylacetic acid amide series, which contain one or two water-solubilizing groups of the series of the carboxylic acid and/ or sulfonic acid groups but no other water-solubilizing groups except the enolizable CO group of the acylacetylamino radical, with compounds of divalent or multivalent metals.

Particularly suitable for the production of the lakes are the monazo dyestuffs of the formula:

A and A represent monoor dinuclear aromatic radical-s,

R alkyl or aryl,

x a carboxylic acid group,

y a sulfonic acid group, and

m and it each stand for one of the figures 0, 1 or 2,

the sum of m and n being either 1 or 2.

wherein These monoazo dyestuffs are produced by the known methods. The acylacetylamino compounds named as coupling components can be, for example, benzoylacetylaminobenzenes or naphth-alenes, or more especially acetoacetylaminobenzenes or naphthalenes. The benzene nuclei of these compounds, which are adjacent to the --NH- groups, may be free of other substituents or may carry one or more further substituents, for example, low molecular alkyl or alkoxy groups such as methyl, ethyl, methoxy or ethoxy groups, halogen atoms such as bromine or chlorine, acetylarnino or benzoylamino groups. The following are listed as examples:

Benzoylacetylaminobenzene, l-benzoylacetylarnino-2-, 3- or 4-methyl, -2-, 3- or 4-methoxy, -2-, 3- or 4- chlorobenzene, acetoacetylaminobenzene,

lacetoacetylaminoQ-chlorobenzene,

1-acetoacetylamino-2-methoxybenzene, 1acetoacetylamino-4-methoxybenzene, lacetoacetylamino-Z-rnethoxy-Smethylbenzene, 1-acetoacetylamino-2.4-dimethylbenzene, l-acetoacetylamino-Z.S-dimethoxybenzene, 1acetoacetylamino-2-methoxy-4-chloro-S-methylbenzene, 1acetoacetylamino-Z-ethoxy-4-chloro-S-methylbenzene, 1-acetoacetylamino-2-methoxy-4-bromo-5-methylbenzene, 1acetoacetylamino-2-ethoxy-4-bromo-5methylbenzene, l-acetoacetylamino-2-methoxy-4 acetylamino5-chlorobenzene, 1acetoacetylamino-Z.5-dimethoxy-4-benzoylaminobenzene,

l-acetoacetylamino-Z.S-dimethoxy 4 chlorobenzene and its sulfonic acid derivatives, and

l-acetacetylaminoor 1benzoylacetylaminonaphthalene- 2-, 4- or 8-sulfonic acid and 2-acetoacetylaminoor 2benzoylacetylaminonaphthalene-1-, -5-, -6-, 7- or 8-sulfonic acid.

tes Patent The following are examples of diazo components used for the production of the monoazo dyestuffs:

acid, acid,

- 1amiuo-4.S-dichlorobenzeneQ-sulfonic acid,

1amino-Z.5-dichlorobenzene-4-sulfonic acid, l-amino-2methoxy-5-methylbenzene-4sulfonic acid, 1amino-Z.4-dimethyl-6-sulfonic acid, 1-amin0naphthalene-2, 4- or 8-sulfonic acid, and 2- arninonaphthalene-l-, -5-, -6-, 7- or 8-sulfonic acid.

In the process as defined above the lakes are formed with the finished dyestuif. However, the coupling reaction giving the monoazo dyestuffs and their combination with metal salts to form lakes can be performed simultaneously. This mode of operation forms a further part of the present invention.

In principle all the soluble compounds of divalent and multivalent metals whose atomic weight exceeds 24 are suitable for the formation of the lakes. Special mention may be made of the compounds of alkaline earth metals, aluminum, manganese, iron, cobalt, nickel, copper, zinc, cadmium and lead. It is advantageous to employ watersoluble salts, either singly or in mixture with the salts of other divalent or multivalent metals, in amounts sufiicient to combine with the carboxylic acid and/or sulfonic acid groups of the dyestuff to give the lake. It is advisable to employ an excess of the metal compound.

For conversion into lakes the above-defined monoazo dyestuffs are dissolved or suspended in water. As stated above, the lakes can also be formed in the coupling mixture in which the dyestuffs have been produced. When this latter procedure is followed the coupling mixture is adjusted to the optimum pH value, e.g. 6.5 to 7.5, and

the solution of the metal compound or mixture of metal compounds is added. The treatment may be carried out at room temperature, but higher temperatures, for example 70 to C. and above, are'preferable. The choice of a suitable temperature is important, because it has an eifect on the color and the fastness properties of the lake. After a short time the lake so formed is precipitated from the solution or suspension and filtered off. i

If the mode of operation involving simultaneous coupling and lake formation is adopted, the coupling reaction is conducted in a medium rendered alkaline with a hydroxide of the metal'used for laking' and, if desired, an addition of an alkali metal hydroxide. Alternatively, the diazo solution or suspension can be mixed with the solution of the appropriate metal salt and the mixture then run into the solution or suspension of the coupling component preferably at temperatures below 20 C. Following this, the formed color lake is filtered off, or the mass is adjusted to a suitable pH-value, heated if desired and the formed color lake is filtered off.

The filter cakw, either in the moist state or after intermediate drying, are ground to bring them into a form suitable for further processing. Grinding is carried out to best efiect in presence of a dispersing agent, binder or plasticizer. i

To impart a soft texture to the lakes it is advantageous to employ interfacially active substances in their production, e.g. soap, alkylarylsulfonates, sulfonated fatty alcohols, rosin soap, and fat or oil emulsions. A suitable filler may also be included in the mass; examples are aluminum oxide, titanium dioxide, barium sulfate or lead sulfate.

The lakes of the monoazo: dyestuffs which are obtained by the present process possess outstanding light fastness,

migration.

a good migration fastness in polyvinyl chloride in presence of plasticizers and good resistance to heat in polyvinyl chloride and other plastics; they are practically insoluble .in the solvents used in the industry of lacker and prints;

The filter cake of the monoazo dyestuff which is obtained by coupling the diazo compound of 22.1 parts of 1-amino-5-methyl-4-chlorobenzene-Z-sulfonic acid with 20.7 parts of l-acetoacetylamino-Z-methoxybenzene is mixed with 3000 parts of water. The suspension is neutralized and after heating to 80 a solution of 9 parts of anhydrous calcium chloride in 500 parts of Water at 80 is added in the course of about 15 minutes. The whole is maintained at 80 for 1 hour, after which the lake is filtered off and dried in vacuo at 60.

The lake dyes polyvinyl chloride in the mass a greenish yellow.

If conditions different from the above are employed,

e.g.. lower or higher temperature and/or different pH values, the resultant lakes are similar to that of the above example but may show slight deviations of shade.

The mono-azo dyestuffs are produced in the following way: 22.1 parts of 1-amino-5-methyl-4chlorobenzene-2- sulfonic acid are dissolved in 500 parts of water with the aid of 15 parts of 30% caustic soda. After filtering off the undissolved substance, a solution of 6.9 parts of sodium nitrite in 100 parts of water is added. The resultant mixture is dropped at 5-6 over a period of 30 minutes into a mixture of 25 parts of 36% hydrochloric acid and 100 parts of water. After this time the mass is stirred for 2 hours at 5-6.

Meanwhile 20.7 parts of l-acetoacetylamino-2-methoxybenzene are dissolved in 200 parts of water'and 15 parts of 30% caustic soda. The undissolved substance is filtered off'and a solution of 50 parts of crystallized sodium acetaterin 75 parts of water is added to the filtrate, followed by sufficient 10% acetic acid to cause the mixture to react weakly acid to litmus paper.

In the course of 30 minutes the diazo suspension at 20-30 is run into the solution of the coupling component and kept in constant agitation overnight. n the following day the monoaz o dyestufi formed is filtered oil? at 60 and washed with Water. g

The procedure for dyeing polyvinyl chloride in the mass is as follows.

0.1 part of'the pigment dyestufi described in the present example is wetted out with 1 part of dioctyl p-hthalate and pasted with a spatula. 100 parts of a previously prepared mixture of 60 parts of polyvinyl chloride, 40 parts of d ioctyl phthalate' and the commonly used stabilizing agents are mixed with the paste. The mixture is gelatinized on a roller for 10 minutes at 140-150 and the gel pressed in to film between polished metal plates heated to about 140; The filmis colored in a shade of greenish yellow which shows excellent fastness to light and g p Example 2 V The filter cake of the monoazo dyestulf of the diazo compound of 22.1 parts of l-amino-5-methyl-4-chlorobenz'ene-Z-sulfonic acid and 27.2 parts of l-acetoacetylamino 2.5-dimethoxy-4chlorobenzene is suspended in 5000 parts of water. After neutralization, the suspension is heated to 95 and over the next 30 minutes a solution of 9 parts of anhydrous calcium chloride in 500 parts of water at 95 is added. The whole is. maintained at 95 for a further 45 minutes, then the formed lake is filtered off and dried in vacuo at 60. It dyes polyvinyl chloride yellow in the mass.

The monoazo dyestuif used as starting material is produced as follows: 22.1 parts of l-amino-5-methyl-4- chlorobenzene-Z-sulfonic acid are diazotized. as described in Example 1. At the same time 27.2 parts of l-acetoacetylamino-2.5 -di1nethoxy-4-chlorobenzene are dissolved in 400 parts of water and 15 parts of 30% caustic soda. After filtering to remove undissolved substance, a solution of parts of soda in 100 parts of water and 100 parts of pyridine is added to the filtrate and the whole is cooled to 5.

The diazo suspension is added to the solution of the coupling component at about 5 in the course of 2 hours. The mixture is agitated overnight and on the following day is heated to 60, the precipitated monoazo dyestuif then being filtered off.

A nitrocellulose lacquer is produced as follows: 2 parts of the pigment dyestufr' obtained as described inthe first paragraph of the process of Example 2 are ground with 100 parts of a commercial nitrocellulose lacquer medium in a ball mill until a sample viewed in the microscope is found to contain no particles larger than 1,11,. The lacquer can be applied by a spraying or dipping technique to give coatings of good fastness to light and good resistance to top finishes and solvents.

Example 3 When the 9 parts of anhydrous calcium chloride used for the production of the lake in Example 1 are replaced by 25 parts of anhydrous lead nitrate or 11 parts of anhydrous manganese sulfate or 9 parts of anhydrous aluminum sulfate or 21 parts of crystallized ferrous sulfate or 14 parts of crystallized ferric chloride or 19 parts of crystallized cadmium or copper sulfate or 21 parts of crystallized nickel or cobalt sulfate or 9 parts of anhydrous magnesium sulfate or 10 parts of anhydrous zinc chloride or 18 parts of crystallized barium chloride or 20 parts of crystallized strontium chloride, color lakes are obtained with the same shade and the same excellent fastness properties as the calcium lake described in Example 1.

Example 4 7 When 18 parts of crystallized barium chloride are employed in placed the 9 parts of anhydrous calcium chloride of Example 2, a yellow barium lake is produced which is highly suitable for the mass pigmentation of cellulose acetate and triacetate.

A mixture of 100 parts of Cellit (secondary cellulose acetate with a content of 54-55% of splittable acetic acid), 400'parts of acetone and 1 part of the pigment dyestufl described in the present example is ground in a ball mill. Grinding is continued until the bulk of the particles in a film formed by pouring a sample on to glass is found to be not larger than 1 The yellow shade of the spun filament is outstandingly fast to light and withstands all the normal treatments without loss of depth. It also shows verygood fastness to washing, perspiration, gas fumes, cross dyeing, hydrosulfite, oxalic acid, peroxide bleaching, alkaline chlorine bleaching and dry cleaning.

Example 5 The filter cake of the monoazo dyestufi obtained by coupling the diazo compound of 22.3 parts of Z-aminonaphthalene-l-sulfonic acid with 27.2 parts of l-acetoacetylamino-2.5-dimethoxy-4-chlorobenzene is suspended in 3000 parts of water in presence of 5 parts ofa sulfonated fatty alcohol. The suspension is heated to 75 and in the course of 20 minutes a solution of 4 parts of anhydrous calcium chloride and '7 parts of crystallized barium chloride in 500 parts of water at 75 is added. The whole is agitated for a further hour at C., then the color lake so formed is filtered oil, washed water and dried wi h vacuum at 6Q. Example Diazo Component Coupling Component Metals for Lake The color lake dyes polyvinyl chloride in yellow shades Formatwn which are fast to light and sublimation.

A printing ink is prepared in the following manner: 5 31 l-acetoacetylaminobenzene. Pb, Mn, Zn,

1 part of the pigment dyestuff described in the first para- Al.

graph of this example and parts of aluminum hydrate 32 are compounded with a suitable quantity of a linseed oil 2-su1fonic i A1.

vehicle in a three-roller mill until a printing ink of the 33 i sgfifiglf k g g desired consistency is produced. The ink obtained in this 34 do l-acetoacetylarnino- Ca, Ba, Pb,

way gives yellow prints on paper which have good fast- 35 do Ca g g ness to light and overprinting. benzepaacar. M i i,

In the following table further color lakes are listed 36 l amino z methyl4 gg acid- 0a Ba Pb which can be produced by the procedures described in 37 chorobenzene. t M Z ,'N1.

' 0 -ace 0308 Y ammoa, a,

the foregoing ei ramples. They are characterized by the benzene+sulfonic Mn, Zn, N1.

diazo and coupling components of the monoazo dyestufis acid,

used for their production. The lakes produced with the 38 Zg g% f3 22 58323 3; E Z

metals Mg, Ca, Sr, Ni, Ba, Zn, Cd, Pb, A1, C0, Cu, Fe 39 1-amino-4-methoxydo Ca, Ba, Pb,

and Mn color polyvinyl chloride in greenish yellow shades gg jf of very good fastness to light and migration. 40 l-amino-t-chlorol-benzoylacetylami- 0a, Ba, Pb,

benzene-Z-sulfonic nonaphthalenei- Mn, Zn, Ni. acid. sulfonic acid. 41 1-amino-2A-dimethl-acetoacetylamino- Ca, Ba, Pb,

Iylbenrenie-fi-sulpaphthaene-B-sul- Mn, Zn, Ni.

E l D'az C m onent Cou lin Com orient Metals for Lake onic aci onic aci N Z P e 1 0 0 p p g p Formation 42 l-aminonalphthah l-zcegaoeglamino- 021 ;I Ba,Z Pb,N

ene- -Sl1 OHIO -0 01'0 enzene. H n 1. acid. I J 6 l-aminobenzene-2- l-acetoacetylamino- Mg, Sr, Ca, carboxylic acid. 2.5-dimethoxy-4- Ba, Zn, Pb,

chlorobenzene. MMn,SCd. 7 "ii%i' 53, git; Having thus disclosed the invention what we claim is: 1. Color lakes of monoazo dyestuffs of the formula 8 l-aminobenzenei- -do Mg, Sr, Ca,

carboxylic acid 1131a, Zni Pb,

9- l-aminoben Pne-2- fin Mg, 5 C H CH3 E sulfonic acid. gla, Zeni Pb, 310! 11,

10 l-aminoben ene-S- dn Mg, Sr Ca sulfonic acid. Ba, Zn, Pb AONN EH COTNH D d MMn,SCd. C l

11 l-aminobcnzenet- 0 g, r, a,

sulfonic acid. Ba, Zn, B lower alkyl Mn, Cd.

12 1-amino-4-methy1 do M S r, Ga,

2 d fg, 6 i S whferein t(Zach of A and B reprfeslenctii a mem llliler selecteg 13 -l l-aminot-met yl-5- 0 g, a r i chlorobenzene z Ba mi? 1 e group consisti g o y ogen, c or e, an sulionic acid. Cd, Mn, Ni, me Y 83 Fe, D represents a member selected from the group con- 14 l-amiuo-4.5dichloro do Mg, 'oa, Sr, sisting of hydrogen, chlorine and bromine;

bellezenw'suliomc Pb, E represents a member selected from the group conand. 8 21 2 sisting of hydrogen chlorine bromine lower alkyl 15 Lammoajmcmow Mg, Ca, Sr, and lower alkoxy, and the metals used forthe lak benezene-l-sulfonic Ba, Zn, Pb, formation being selected from the group consisting acld- 8g & of an alkaline earth metal, aluminum, manganese,

Cu. iron, cobalt, nickel, copper, zinc, cadmium and lead. 16 i i 2. The yellow color lake consisting essentially of a 2-suifomc 1016,. Be, Zn, Pb,

8d, 151, 1 m, Water-msoluble metal compound of the monoazo dyestuif formed by coupling 1-diazo-4-methylbenzene-2-sulfonic 17 1-amin0benZene-2- l-acetoacetylamino- Ca, Ba, Pb, acid with 1-acetoacetylam1no-2.5-d1methoxy-4-chloroben- 18 gggg g f gggg 2' fi"fff 3 3 2 4, zene, the metal being a multivalent lake-forming metal carboxylic acid. Mn, Zn. selected from the group consisting of an alkaline earth 19 'igi gggfggigig- IQ fiZ metal, aluminum, manganese, iron, cobalt, nickel, copper,

20 1-a inobenzene-2- do Ca, Ba, Pb, zinc, cadmium and lead.

21 Nude Ca, 15 3- A yellow color lake consisting essentially of a water- 3-sulfonic acid. d G g, 1 insoluble alkaline earth-metal salt of the monoazo dye- 22 stufi formed by coupling l-diazo-S-methyl-4-chloroben- 23 l-aminoei-mcthyla a zene2-sulfonic acid with 1-acetoacetylarnino-2.S-dirnethbenfcne-Z-sulfonlc 11, Zn. oxy 4 chlorobenzene 801 24 l-aminH-methyl- Ca, Pb, 4. A yellow color lake consisting essentially of a water 2' insoluble metal compound of the monoazo dyestuff -su 0111C 8C1 25 -z g g 3 3 1 5 I formed by coupling 1-diazo-4-methyl-5-chlorobenzene-2- 1253 53 33?" sulfonic acid with l-acetoacetylamino-2.5-dimethoxy-4- 26 l-amino C31 Pb, chlorobenzene, the metal being a multivalent lake-forming 1' metal selected from the group consisting of an alkaline 27 0573mm), earth metal aluminum manganese iron cobalt nickel chloro-benzene- :1, Zn. 4-sulfonic acid, copper, 2111C, cadmium and lead.

3 ,2 5'. yellow color lake consisting essentially of the aci water-insoluble alkaline earth metal salts of the monoazo l-aminobenzenel-acetoacetylamino- Mg, Ca,Cd,

2 Su1f0nic acid naphtha1ene Ba Pb dyestuff formed by couplmg l diazo 4 methyl 5 chloro 0.--- 2-acetoacetyla1m'no- Mg,Ca,Cd, benzene-Z-sulfomc acid With 1-acetoacetylam1no-2.S-dinaphthalenemethoxy-4-chlorobenzene.

6, A yellow color lake consisting essentially of awater insoluble metal compound of the monoazo dyestufi formed by coupling 1-diazo-4.S-dichlorobenzene-Z-sulfonic acidwith 1-acetoacetylamino-2L5-dimethoxy-4-chlorobenzene, the metal being a multivalent lake-forming metal selected from the group consisting of an alkaline earth metal, aluminum, manganese, iron, cobalt, nickel, copper, zinc, cadmium and lead.

7. A yellow color lake consisting essentially of a waterinsoluble metal compound of the monoazo dyestufi formed by coupling 1-diazo-4-methyl-5-chlorobenzene-2- sulfonic acid with l-acetoacetylamino-Z-methoxybenzene, the metal being a multivalent lake-forming metalselected from the group consisting of an alkaline earth metal, aluminum, manganese, iron, cobalnnickel, copper, zinc, cadmium and lead.

References Cited in the file of this patent UNITED STATES PATENTS 1,086,155 Geldermann et a1 Feb. 3, 1914 1,126,413 Desamari Jan. 26, 1915 1,788,299 Huismann et al Jan. 6, 1931 2,092,796 Black Sept. 14, 1937 2,203,038 Zitscher et al June 4, 1940 2,229,049 Dahlen et al Jan. 21, 1941 2,626,255 Blumenthal Jan. 20, 1953 FOREIGN PATENTS 575,787 Germany May 3, 1933 OTHER REFERENCES Geigy: German application Ser. No. Gl6457 1V b/ 22a, printed August 30, 1956, K1. 22211 (pages 1 and 2 relied upon). 

1. COLOR LAKES OF MONOAZO DYESTUFFS OF THE FORMULA 